Hydrogenating and deodorizing edible oils



Sept. 5, 1950 R. H. POT-rs ETAL 2,521,602

HYDROGENATING AND nEoDoRIzING EDBLE oILs Filed Feb. 25, 1945 Patented Sept. 5, 1950 HY DROGENATING AND DEODORIZING EDIBLE OILS Ralph H. Potts, La Grange, and Charles E. Morris, Chicago, Ill., assignors to Armour and Company, Chicago, Ill., a corporation of Illinois Application February 23, 1945, Serial No. 579,464

6 Claims.

This invention relates to treating edible oils and the like. The new method will be found applicable to other uses. The present application constitutes a continuation-in-part of our copending application Serial No. 425,284, now abandoned, filed January l, 1942, for Treating Edible Oils.

In the hydrogenation of edible oils through the use of removable catalysts, as now commonly practiced, the oil is mixed with the catalyst, hydrogenated under elevated temperatures and pressures, chilled and then filtered. Subsequently, the filtered stock is re-heated to deodorize it. The oil has to be cooled ybefore the filtering stage because it is found that when heated oil containing the catalyst is brought into contact with air, discoloration of the oil results.

An object of the present invention is to provide a method wherein the operation may vbe carried on continuously without interruption and wherein the heat resulting from the hydrogenation operation is utilized later in the deodorizing steps. A further object is to provide a continuous process in which the dissolved hydrogen carried by the oil leaving the hydrogenation unit is released under vacuum in the deodorizing step for the removal of impurities. A further object is to provide a process in which hydrogenation, filtering out the removable catalyst and deodorizing of the oil, is accomplished in a continuous operation with a saving in heat and with the carrying over of the results of one operation into a subsequent operation to aid the latter.

Another object of the invention is to provide for the selective hydrogenation of oils and similar materials so as to produce a substantially uniform product in which only partial hydrogenation is accomplished. Still a further object is to provide for the hydrogenation of the stock by reacting the stock in the liquid phase with hydrogen in the presence of a removable catalyst.

Other specific` objects and advantages will appear as the specification proceeds.

The invention is illustrated, in a preferred embodiment, by the accompanying drawing in which the single figure represents, diagrammatically, apparatus suitable for carrying out the process.

Broadly, the invention comprises a continuous process involving continuous hydrogenation and including mixing an edible oil or other suitable charging material with a catalyst which may be removed -by filtration, hydrogenating the oil under elevated temperatures and pressures and in the presence of the catalyst, passing the hot oil into a degassing tank where under reduced pressure and elevated temperature, the dissolved hydrogen within the oil is removed, carrying with it impurities in the oil. The oil is further treated by heat and steam to strip oil the volatile odoriferous fractions. The catalyst is removed by filtration at any desired point. The final product may be chilled and packaged.

In the invention, the oil or other suitable charging stock is mixed with a catalyst to form a substantially uniform and homogeneous mixture of catalyst and oil, and this mixture is passed in a stream into a zone where it is treated with hydrogen to accomplish the hydrogenation.

As a specific illustration of the method, the following may be stated in connection with the apparatus illustrated. The oil enters pipe Il under the influence of the proportioning pump I I. Catalysts contained within the tanks I2 and I3 are passed through pipe I 4- into the line I5. The catalyst may be any suitable material adapted to be removed by filtration. Since such catalysts are well known, a detailed description is not needed. As a specific example, nickle catalyst may be employed.

Hydrogen is introduced through the line It. The hydrogen and oil pass upwardly through pipe I1 into the jacketed hydrogenator I8, which is of well-known construction. Communicating with the interior of the hydrogenator I8 is a tank I8 provided with a vent Ipipe 20. The tank I9 communicates with the hydrogen space in the hydrogenator through the overflow pipe 2l and with the liquid space in the hydrogenator through the overflow pipe 22.

The substantially uniform mixture of oil and catalyst is thus passed in a stream into the hydrogenator and subjected substantially uniformly to treatment with hydrogen to perform the` selective hydrogenation of the material. The reaction is a. reaction between the oil and the liquid phase and the hydrogen.

Instead of passing the mixed oil and catalyst directly into the hydrogenator, we can introduce this mixture to a heated vacuum chamber to removi` moisture andV gases and then -pass the deacrntcd material into the hydrogenator. l

From the hydrogenator, the oil flows through closed line 23 to the filters 24, which exclude air. Though lters of this type may be slightly more inconvenient in operation. we have found that filters of this type play an important part in our new process.

From the lters, the oil flows through the valvecontrolled lines 25 and 26 in line 21, which opens into the top portion of the degassing tank 28.

The lower portion of the tank 28 is provided with a heating coil 29 through which a heating fluid. such as a mixture of diphenyl and diphenyl oxide. or any other suitable heating uid may be passed to heat the oil. Also, the bottom portion of the tank 29 is provided with a steam pipe 30 through which steam may be introduced into the oil. Degassing tank 28 is maintained under reduced pressures by the vacuum line 3| which leads to a barometric condenser 32. Since the barometric condenser 32 and the associated vacuum pumps are of well-known construction, a detailed description is believed unnecessary.

Oil leaving the degassing tank 28 passes through the valve-controlled pipe 33 into the deodoriztiug column 34. The deodorizing column 34 is also maintained under reduced pressure by a pipe connection 35 leading to the barometric condenser 32. The oil is introduced into the top portion of the stripping or deodorizing column 34 and it flows downwardly over successive baffles to the bottom of the tower, meeting as it descends n counter-dow of steam which assists in the removal of the undesirable volatile fractions. The steam is introduced into the bottom of the column through pipe 36.

Oil leaving the column 34 passes through line 31. pump 38 and pipe 39 into a coil 40 in the lower portion of a steam generator 4i. Heat is withdrawn from the coil 40 to form steam and the steam after leaving the generator is superheated in the heat exchange unit 42, the heating fluid being passed through lines 48 and 44.

The oil leaving the coil 40 in the heat exchanger passes through pipe 45 and branched valve-controlled lines 48 and 41 into the lters 48 where any remaining unremoved portions of the catalysts are recovered. The oil then passes through valved lines 49 and 50 and the conduit 5| into the holding tank 52 from whic-h it is withdrawn for chilling and packaging.

Temperature and pressure conditions in the various parts of the apparatus may vary considerably. In the specific illustration given, the I oil was introduced through supply line I at a temperature of 150 F. In the hydrogenator, the temperature was in the neighborhood of 300 F. and the pressure varied from to 75 pounds. rl'he pressure extended beyond the lters 24 to the pressure valves in lines and 26 and was in the neighborhood of from 3 to 5 pounds at these points.

Within the degassing tank, the pressure was reduced below 50 mm. of mercury and preferably was about one inch mercury absolute. The temperature within the degassing tank was in the neighborhood of 400 F. While it is desirable to have the pressure extend through the filters 24, as already described, and even through filters 48, it will be understood that such pressure may not be necessary.

In the operation of the process, the mixed catalyst and oil, together with the introduced hydrogen. are brought into the hydrogenator I8 in which hydrogenation occurs, a considerable quantity of hydrogen dissolving, as free hydrogen, in the oii. Hydrogen is permitted t0 escape when this is desired, through the valve-controlled line 20. The heated cil passes through the continu ous filters 24, pressure being reduced to atmospheric within the filters or slightly beyond. We prefer to hold a. slight amount of back pressure upon the ltcrs by means of the valves in lines 25 and 26. These valves serve a very important function in connection with the closed type of filters used in this process in that they serve to prevent the reduced pressure maintained in the degassing tank 28 from extending into the filters, thus avoiding. the possibility of air leading into the filters from the outside. The oil leaving the filters and with its contained hydrogen passes through line 21 into the tank 28. Here the pressure is very sharply reduced so that the hydrogen is free to escape, together with the impurities carried by it. In addition, heat and steam are employed to further remove volatile material. A counter-current stripping action is carried on within column 34 which is also maintained under reduced pressure and where superheated steam is utilized. A further filtration may be carried on within the filters 48. This filtration step may be found to be unnecessary and may be omitted. If desired, the rst filtration step in which filters 24 are employed may be omitted and the filtration accomplished solely in lters 48. Throughout the entire process, air is excluded from the apparatus, the apparatus being maintained alternately under pressure and partial vacuum.

In the operation in which the lters 24 are omitted and the filtration performed solely by the final filters 48, it is found that more satisfactory results are obtained. The filters 48 eliminate not only the catalyst, but also impurities, so'

that the product is then passed directly through the conduit 5I to storage tank 52 Without being brought into contact with the air. From the tank 52, the product is preferably passed into a continuous chilling and texturating device and filled into containers which are hermetically sealed without being brought into contact with air. Thus, the entire operation from the hydrogenation step through to the packaging of the nal product is carried out in the absence of air.

After the hydrogenation operation, the stream of liquid containing the absorbed free hydrogen may be passed directly to the heated and steamequipped tank 28, or, if desired, passed directly to the deodorizing tank 34 and heat and steam employed therein for stripping the oil of the undesirable fractions.

By maintaining the oil in the hydrogenator I8 under substantial pressure created by the hydrogen atmosphere, a substantial amount of free hydrogen is absorbed, and when subsequently the stream of oil is passed into tank 28 and heat supplied thereto, the hydrogen, under the inuence of the heat and the reduced pressure existing in chamber 28, is freed, carrying with it the absorbed impurities and odoriferous material. The influence of the heat and steam brings about a liberation of the absorbed free hydrogen and the odoriferous material carried by it. This function is performed whether the hydrogenated material be passed into chamber 28 or directly into the tower 34.

'Ihe foregoing process in which the oil is saturated with hydrogen gas as it enters the degassing chamber or deodorizing tower and is therein subjected to heat and reduced pressure,

asaneoa results in a product having a much improved color, davor, and stability. All of the reasons for the improvement, from a chemical standpoint, are not fully understood. It may be that the organic impurity is in a, reduced state and in .this condition would naturally be more volatile than it would be when oxidized. It is therefore much more easily removed from the oil by the steam deodorization process than it would be if allowed to oxidize by contact with air after the hydrogenation step and before deodorization, as is usual in ordinary batch practice.

By reason of the treatment of the liquid phase uniform mixture of oil and catalyst with the hydrogen and the uniformity of the reaction, the oil may be selectively hydrogenated so that the linoleic acid is saturated to the extent necessary to form oleic acid without hydrogenating oleic acid to stearic acid to any substantial extent. The uniformity of the reaction also aids in obtaining uniform temperatures throughout the reaction mixture and thus helps in controlling the hydrogenation reaction and also makes it possible to control the tendency of oleic acid to be converted at high temperatures from the cis to the trans form. The resultant product is substantially uniform and homogeneous.

While in the foregoing descriptionof the process, we have set forth certain steps and conditions a desirable in the specific illustrations, it will be understood that such conditions and steps may be varied or carried on in different sequences without departing from the spirit of our invention. We do not desire to be limitedto the exact details of construction shown and described, for obvious modifications will occur to those skilled in the art.

We claim:

l. In a continuous process for treating edible oils, the steps of continuously introducing the oil and a removable hydrogenating catalyst into a hydrogenating zone under a pressure of about 20 to '75 pounds, introducing hydrogen in substantial excess of that required for hydrogenation under the pressure in said zone to cause a considerable amount of free hydrogen to be absorbed in said Oil, heating the oil within said zone to a reactive temperature for hydrogenation, continuously passing the hydrogenated oil while still hot and out of contact with the outside atmosphere to a pressure release zone, subjecting the oil containing free hydrogen in said pressure release zone to heat and pressure below atmospheric to liberate said absorbed free hydrogen and odoriferous materials carried therewith from the oil, and withdrawing a continuous stream of oil from said pressure release zone.

2. In a continuous process for treating edible oils, the steps of continuously introducing oil and a removable hydrogenating catalyst into a hydrogenating zone under super atmospheric pressure in the neighborhood of '75 pounds. introducing hydrogen substantially in excess of that required for hydrogenation/to cause a considerable amount of free hydrogen/ to be absorbed within said oil under the pressure therein, heating the oil Within said zone to a reactive temperature for hydrogenation, continuously passing the hydrogenated oil out ofcontact with the outside atmosphere in a confined stream topressure release zone, subjecting the oil in said pressure release zone to a temperature in the neighborhood of 400 F. to pressure below atmospheric to liberate said absorbed free hydrogen and odoriferous materials carried therewith from the oil, and withdrawing a continuous stream oi.' oil trom'said ypressure release zone.

3. In a continuous process for treating edible oils, the steps of continuously introducing the oil and a removable hydrogenating catalyst into a hydrogenating zone to provide a mixture of oil and catalyst in said zone, maintaining said zone under pressure of about 20 to 75 pounds, introducing hydrogen in substantial excess of that required for hydrogenation to cause said excess of hydrogen to be absorbed in said oil under said pressure, heating the oil within said zone to a reactive temperature for hydrogenation, continuously filtering the hydrogenated oil in a conilned zone out of contact with the outside atmosphere to remove the catalyst, continuously passing the filtered hydrogenated oil still out of contact with the outside atmosphere and while still hot to a pressure release zone, and subjecting the oil in said pressure release zone to pressure below atmospheric to liberate absorbed free hydrogen and odoriferous materials in the oil carried thereby, and withdrawing a continuous stream of oil from said pressure release zone.

4. In a continuous process for treating edible oils, the steps of continuously introducing the oil and a granular catalyst into a hydrogenating zone from which air is excluded to provide a mixture of oil in catalyst in said zone, maintaining said zone under a pressure of about 75 pounds per square inch, introducing hydrogen into said zone in substantial excess of that required for hydrogenation to cause free hydrogen to be absorbed in said oil under said pressure, heating the oil to a reactive temperature for hydrogenation, continuously iiltering the hydrogenated oil in a confined stream out of contact with outside atmosphere to remove the catalyst, continuously passing the ltered hydrogenated oil while still out of contact with outside atmosphere and while still hot to a pressure release zone, and subjecting the oil containing said free hydrogen in said pressure release zonevto pressure below atmospheric and in the absence of air for the liberation of said absorbed free hydrogen and odoriferous materials carried thereby in the oil, and withdrawing the oil from said pressure release zone.

5. In a continuous process for treating edible oils, the steps of continuously introducing the oil and a removable hydrogenating catalyst into a hydrogenatin-g zone under a pressure of about 20 to 75 pounds, introducing hydrogen in substantial excess of that required for hydrogenation to cause the same to be absorbed in said oil under said pressure, heating the oil within said zone to a temperature of about 300 F., continuously passing the hydrogenated oil while still hot and out of contact with the outside atmosphere to a deodorizing zone, reducing the pressure in said deodorizing zone below 50 mm. of mercury to liberate said absorbed free hydrogen and the odorlferous material carried therewith from the oil, and withdrawing a continuous stream of oil from said deodorizing zone.

6. In a continuous process for hydrogenating of edible oils and the deodorizing thereof, the steps of continuously introducing the oil and a removable hydrogenating catalyst into a hydrogenation zone under a pressure of about 20 to '75 pounds, introducing hydrogen in dsubstantial excess of that required for hydrogenation to cause the same to be absorbed in said oil under said pressure, heating the oil within said zone to a reactive temperature for hydrogenation, continuously passing the hydrogenated oil while still hot 7 8 to a deodorizing sone. reducing the pressure in UNITED STATES PATENTS said deodorixing zone to about 1" mercury abso- Number Na Date lute t0 liberate Said absorbed free hydrogen and 2 207 712 Blaso .m July 16' 1940 odoriferous material carried therewith from the '2307'065 'Paterson Jan. 5 19 oil, and withdrawing a continuous stream o! oil 5 23513332 Neal June 20:19 from Said www 0m- 2,3s5,o45 orxowski Dee. 12, 1944 RALPH H, POTIS, 7 OTHER REFERENCES CHARLES E- M0RR1S lo Dean, "Utilization of Fats," pages 123 and 124,

Harvey, London, 1938. REFERENCES CITED Brockiesby. The Chemistry and Technology of The following .references are 0f record in the Marine Animal Oils," Fisheries Research Board file 0f this Dnt of Canada, Bulletin LIX, page 280, 1941. 

1. IN A CONTINUOUS PROCESS FOR TREATING EDIBLE OILS, THE STEPS OF CONTINUOUSLY INTRODUCING THE OIL AND A REMOVABLE HYDROGENATING CATALYST INTO A HYDROGENATING ZONE UNDER A PRESSURE OF ABOUT 20 TO 75 POUNDS, INTRODUCINT HYDROGEN IN SUBSTANTIAL EXCESS OF THAT REQUIRED FOR HYDROGENATION UNDER THE PRESSURE IN SAID ZONE TO CAUSE A CONSIDERABLE AMOUNT OF FREE HYDROGEN TO BE ABSORBED IN SAID OIL, HEATING THE OIL WITHIN SAID ZONE TO A REACTIVE TEMPERATURE FOR HYDROGENATION, CONTINUOUSLY PASSING THE HYDROGENATED OIL WHILE STILL HOT AND OUT OF CONTACT WITH THE OUTSIDE ATMOS- 